EP1785773A1 - Kristallines Wachs - Google Patents

Kristallines Wachs Download PDF

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Publication number
EP1785773A1
EP1785773A1 EP06123677A EP06123677A EP1785773A1 EP 1785773 A1 EP1785773 A1 EP 1785773A1 EP 06123677 A EP06123677 A EP 06123677A EP 06123677 A EP06123677 A EP 06123677A EP 1785773 A1 EP1785773 A1 EP 1785773A1
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European Patent Office
Prior art keywords
wax
percent
crystallinity
resin
acid
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EP06123677A
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English (en)
French (fr)
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EP1785773B1 (de
Inventor
Raj D. Patel
David J. Sanders
Tie Hwee Ng
Stephan V. Drappel
Sandra J. Gardner
Sonja Hadzidedic
Louis V. Isganitis
Timothy L. Lincoln
Kevin F. Marcell
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Xerox Corp
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Xerox Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/06—Other polishing compositions
    • C09G1/08—Other polishing compositions based on wax
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/04—Fractionation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08775—Natural macromolecular compounds or derivatives thereof
    • G03G9/08782—Waxes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08797—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene

Definitions

  • the present disclosure is generally related to distilled or fractionated waxes referred to herein as wax or waxes that can be used in toners, and more specifically, to toners made by emulsion aggregation (EA) and coalescence processes.
  • the waxes herein are crystalline waxes, and have a degree of crystallization.
  • the resulting toners can be selected for known electrophotographic, electrostatographic, xerographic, and like imaging processes, including copying, printing, faxing, scanning, and like machines, and including digital, image-on-image, color, lithography, and like processes.
  • toners In reprographic technologies, such as xerographic and ionographic devices, it is desired to provide toners with high gloss. It is also desired to provide toners that can be used in an oil-less environment, and at low minimum fusing temperatures. It is further desired to provide toners that can be used in high-speed printing and/or copying and the like, machines.
  • Toners in accordance with embodiments herein provide desired fusing characteristics including, for example, release characteristics such as a stripping force of less than about 30 to less than about 5 grams of force; blocking characteristics such as a high blocking temperature of about 45°C to about 65°C; document offset characteristics such as a document offset of about 2.0 to about 5.0; vinyl offset characteristics such as a vinyl offset of about 3.0 to about 5.0; and triboelectrical charging characteristics.
  • release characteristics such as a stripping force of less than about 30 to less than about 5 grams of force
  • blocking characteristics such as a high blocking temperature of about 45°C to about 65°C
  • document offset characteristics such as a document offset of about 2.0 to about 5.0
  • vinyl offset characteristics such as a vinyl offset of about 3.0 to about 5.0
  • triboelectrical charging characteristics triboelectrical charging characteristics.
  • toners in embodiments herein enable the use of lower minimum imaging fusing temperatures, such as from about 120°C to about 170°C, enable high speed printing such as for machines
  • the present toners in embodiments, enable high image gloss, such as in an oil-less fuser system, while still retaining a high blocking temperature, high image gloss comprising of for example from about 30 to about 80 gloss units (GGU) as measured by the Gardner Gloss metering unit; for example on a coated paper, such as Xerox 120 gsm Digital Coated Gloss papers.
  • GGU gloss units
  • toner preparation processes comprising: (i) preparing, or providing a colorant dispersion; (ii) preparing, or providing a functionalized wax dispersion comprised of a functionalized wax contained in a dispersant mixture comprised of a nonionic surfactant, an ionic surfactant, or mixtures thereof; (iii) shearing the resulting mixture of the functionalized wax dispersion (ii) and the colorant dispersion (i) with a latex or emulsion blend comprised of resin contained in a mixture of an anionic surfactant and a nonionic surfactant; (iv) heating the resulting sheared blend of (iii) below about the glass transition temperature (Tg) of the resin particles; (v) optionally adding additional anionic surfactant to the resulting aggregated suspension of (iv) to prevent
  • Emulsion/aggregation/coalescence processes for the preparation of toners are illustrated in a number of Xerox patents, the disclosures of each of which are totally incorporated herein by reference, such as U.S. Patent 5,290,654 , U.S. Patent 5,278,020 , U.S. Patent 5,308,734 , U.S. Patent 5,370,963 , U.S. Patent 5,344,738 , U.S. Patent 5,403,693 , U.S. Patent 5,418,108 , U.S. Patent 5,364,729 , and U.S. Patent 5,346,797 ; and also of interest may be U.S.
  • U.S. Patent 5,922,501 describes a process for the preparation of toner comprising blending an aqueous colorant dispersion and a latex resin emulsion, and which latex resin is generated from a dimeric acrylic acid, an oligomer acrylic acid, or mixtures thereof and a monomer; heating the resulting mixture at a temperature about equal, or below about the glass transition temperature (Tg) of the latex resin to form aggregates; heating the resulting aggregates at a temperature about equal to, or above about the Tg of the latex resin to effect coalescence and fusing of the aggregates; and optionally isolating the toner product, washing, and drying.
  • Tg glass transition temperature
  • U.S. Patent 5,482,812 describes a process for the preparation of toner compositions or toner particles comprising (i) providing an aqueous pigment dispersion comprised of a pigment, an ionic surfactant, and optionally a charge control agent; (ii) providing a wax dispersion comprised of wax, a dispersant comprised of nonionic surfactant, ionic surfactant or mixtures thereof; (iii) shearing a mixture of the wax dispersion and the pigment dispersion with a latex or emulsion blend comprised of resin, a counterionic surfactant with a charge polarity of opposite sign to that of said ionic surfactant, and a nonionic surfactant; (iv) heating the above sheared blend below about the glass transition temperature (Tg) of the resin to form electrostatically bound toner size aggregates with a narrow particle size distribution; (v) adding additional ionic surfactant to the aggregated suspension of (iv) to ensure that no,
  • U.S. Patent 5,622,806 describes a process, for example, for the preparation of toner compositions with controlled particle size comprising (i) preparing a pigment dispersion in water, which dispersion is comprised of a pigment, an ionic surfactant in amounts of from about 0.5 to about 10 percent by weight to water, and an optional charge control agent; (ii) shearing the pigment dispersion with a latex mixture comprised of a counterionic surfactant with a charge polarity of opposite sign to that of the ionic surfactant, a nonionic surfactant, and resin particles, thereby causing a flocculation or heterocoagulation of the formed particles of pigment, resin, and charge control agent; and (iii) stirring.
  • U.S. Patent Application Publication 2004/0130054 A1 discloses waxes used in inks and toners.
  • the waxes have a melting point of 50 to 120°C, and a melting range of 5 to about 65°C.
  • Figure 1 is a DSC curve of heat flow versus temperature for a wax in accordance with an embodiment disclosed herein.
  • Figure 2 is an x-ray diffraction of intensity versus 2-Theta (°) for a wax in accordance with an embodiment disclosed herein.
  • Figure 3 is a graph of viscosity versus temperature and illustrates the useful coalescence temperature ranges and the slope provides a viscosity for a given temperature as defined by an equation in accordance with an embodiment disclosed herein.
  • Figure 4 is a graph of weight percent versus carbon number for a wax in accordance with an embodiment disclosed herein.
  • Embodiments include a distilled wax having from about 30 to about 62 carbon units, a degree of crystallinity as calculated by heat of melting and as measured by DSC of from about 55 to about 100 percent, a Mw of from about 500 to about 800, and a polydispersity (Mw/Mn) of from about 1 to about 1.05.
  • Embodiments also include a crystalline wax having from about 30 to about 62 carbon units, a degree of crystallinity as calculated by heat of melting and as measured by DSC of from about 55 to about 100 percent, an Mw, Mn and Mp all in the range of from about 640 to about 725, and a polydispersity of from about 1 to about 1.05.
  • embodiments include a distilled crystalline wax having from about 30 to about 62 carbon units, a viscosity of from about 100 to about 10,000 centipoise at 92°C, a degree of crystallinity as calculated by heat of melting and as measured by DSC of from about 55 to about 100 percent, an Mw, Mn and Mp all three in the range of from about 640 to about 725, and a polydispersity of from about 1 to about 1.05.
  • a fractionated or distilled wax and more specifically, a crystalline wax, and a toner comprising the wax.
  • the wax can be selected from, for example, a polyolefin wax, an alkylene wax, a polyethylene wax, a polypropylene wax, a paraffin wax, a Fischer Tropsch wax, microcrystalline wax, carnauba wax, jojoba wax, rice wax, beeswax, montanic acid ester wax, castor wax, or mixtures thereof.
  • the wax is a polyethylene wax or a Fischer Tropsch wax, and in specific embodiments, fractionated, crystalline, and/or distilled polyethylene wax.
  • the polyethylene wax in embodiments, is derived from ethylene polymerization.
  • the wax can be prepared using different catalysts including Ziegler-Natta, Fischer Tropsch, metallocene, and like catalysts. Details of how the wax can be made can be found in U.S. Patent Application Publication No. US 20050130054 A1 and U.S. Patent 5,500,321 , the subject matter of which is hereby incorporated by reference in the entirety for both of these references.
  • the number of carbon units for the wax ranges from about 30 to about 62 carbons, and the peak from about 42 to about 55. At 30 carbon units, the weight percent is at about 0.5 weight percent; while at 60 carbon units, the weight percent is at about 0.5 weight percent.
  • the peak weight percent is less than or equal to 20 percent, or from about 1 to about 15 percent, as measured by a gas chromatograph.
  • Figure 4 represents a schematic of the distribution as well as peak ranges of the repeating carbon units.
  • the wax has a degree of crystallinity (Xc) as calculated by heat of melting or heat of fusion or enthalpy, and as measured by DSC, of from about 55 to about 100 percent, or from about 60 to about 98 percent, or from about 70 to about 95 percent, or from about 75 to about 90 percent.
  • Xc degree of crystallinity
  • the heating rate is about 10°C/min and the melting enthalpy is greater than about 150 J/g and measured during the second scan as shown in Figure 1.
  • the percent crystallization is calculated from the following expression:
  • the wax also has a degree of crystallinity as measured on the cooling cycle or heat of recrystallization, of from about 55 to about 100 percent, or from about 60 to about 98 percent, or from about 70 to about 95 percent, or from about 75 to about 90 percent.
  • the crystallinity is measured using the heat of recrystallization, and wherein the degree of crystallinity is calculated using the following formula:
  • the wax has a degree of crystallinity as measured by X-ray diffraction (Xc) of from about 55 to about 100 percent, or from about 60 to about 98 percent, or from about 70 to about 95 percent, or from about 75 to about 90 percent.
  • the temperature is above the resin Tg. Therefore, the temperature range selected results in a viscosity that allows the wax to flow in the resin matrix, allowing for the wax domains to be formed.
  • the wax domains can be larger (for example, from about 0.5 to about 2 microns) than the starting size (for example, from about 0.15 to about 0.8 microns).
  • the useful temperature range for the coalescence/fusion step is from about 92 to about 100°C.
  • Waxes that have the proper flow properties to form the desired wax domains have viscosities that vary as a function of temperature such that they meet the requirements of the following equation: ⁇ cp ⁇ 10 27 - 0.25 ⁇ T ⁇ where ⁇ 92 ⁇ °C T ⁇ 100 ⁇ °C
  • This equation defines the upper bound to the viscosity of waxes, especially fractionated or distilled waxes, over the useful coalescence temperature range (see Figure 3).
  • the wax has a viscosity versus temperature relationship that meets the requirements of the equation.
  • the melt viscosity of the wax for example at 92°C is less than or about 10,000 centipose, or from about 10 to about 10,000 centipoise, and the viscosity at 100°C is less than or equal to 100 centipose, or from about 1 to about 100 centipoise, irrespective of the heating or the melting cycle.
  • the useful temperature for coalescence/fusion step can be lower than 92°C, for example as low as 88°C when the peak carbon number is at less than or equal to 45. This should provide a melt viscosity ( ⁇ ) of less than or equal to 10,000 cps.
  • the wax meets the criteria that fits the equation.
  • the wax meets the enthalpy (Hc) or the recrystallization (Hrc).
  • the wax has an onset temperature of from about 65 to about 70°C, and an offset temperature of from about 95 to about 100°C, during the heat up cycle (i.e., melting), as measured by a DSC when the heating rate is 10°C/min.
  • the needle penetration point of the wax is from about 0.1 to about 10, or from about 0.5 to about 8, or from about 1 to about 5 dmm (decimillimeter).
  • the needle penetration point can be measured in accordance with ASTM 1321, using K95500 Koehler Instruments digital penetrometer, or can be measured in other known ways.
  • the wax in a toner material is present, for example, in an amount of about 6 to about 30 percent, or from about 7 to about 20 percent by weight based upon the total weight of the composition.
  • waxes include those as illustrated herein, such as those of the aforementioned co-pending applications, polyolefins such as polypropylenes, polyethylenes, and the like, such as those commercially available from Allied Chemical and Baker Petrolite Corporation, wax emulsions available from Michaelman Inc. and the Daniels Products Company, Epolene N-15 TM commercially available from Eastman Chemical Products, Inc., Viscol 550-P TM , a low weight average molecular weight polypropylene available from Sanyo Kasei K.K., and similar materials.
  • Examples of functionalized waxes include amines, amides, for example Aqua Superslip 6550 TM , Superslip 6530 TM available from Micro Powder Inc.; fluorinated waxes, for example Polyfluo 190 TM , Polyfluo 200 TM , Polyfluo 523XF TM , Aqua Polyfluo 411 TM , Aqua Polysilk 19 TM , Polysilk 14 TM available from Micro Powder Inc.; mixed fluorinated, amide waxes, for example Microspersion 19 TM also available from Micro Powder Inc.; imides, esters, quaternary amines, carboxylic acids or acrylic polymer emulsion, for example Joncryl 74 TM , 89 TM , 130 TM , 537 TM , and 538 TM , all available from SC Johnson Wax; chlorinated polypropylenes and polyethylenes available from Allied Chemical and Petrolite Corporation, and from SC Johnson Wax.
  • Such waxes can optionally be fractionated or
  • the wax comprises a wax in the form of a dispersion comprising, for example, a wax having a particle diameter of about 100 nanometers to about 500 nanometers or about 100 nanometers to about 300 nanometers, water, and an anionic surfactant or a polymeric stabilize, and optionally a nonionic surfactant.
  • the wax comprises polyethylene wax particles, such as POLYWAX ® 655, POLYWAX ® 850, POLYWAX ® 725, POLYWAX ® 500 (the POLY-WAX ® waxes being commercially available from Baker Petrolite) and, for example, fractionated/distilled waxes which are cuts of commercial POLYWAX ® 655 designated here as X1214, X1240, X1242, X1244, and the like, but are not limited to POLYWAX ® 655 cuts. Waxes providing a specific cut, that meet the viscosity/temperature criteria, wherein the upper limit of viscosity is 10,000 cps and the temperature upper limit is 100°C can be used.
  • the waxes can have a particle diameter in the range of from about 100 to about 500 nanometers, although not limited.
  • Other examples include FT-100 waxes from Shell (SMDA), and FNP0092 from Nippon Seiro.
  • the surfactant used to disperse the wax can be an anionic surfactant, although not limited thereto, such as, for example, Neogen RK ® commercially available from Daiichi Kogyo Seiyaku or TAYCAPOWER ® BN2060 commercially available from Tayca Corporation or Dowfax available from DuPont.
  • the wax has an onset melt temperature of from about 65 to about 75°C, and an offset temperature of from about 95 to about 100°C.
  • the wax has an Mn, Mw and Mp, and each and all may fall within the ranges of from about 500 to about 800, or from about 600 to about 750, or from about 640 to about 725.
  • the wax has a polydispersity (Mw/Mn) of from about 1 to about 1.05.
  • Toners herein can include resins.
  • the resin particles can be, in embodiments, styrene acrylates, styrene butadienes, styrene methacrylates, or polyesters, present in various effective amounts, such as from about 70 weight percent to about 98 weight percent, and more specifically, about 80 weight percent to about 92 weight percent based upon the total weight percent of the toner.
  • the resin can be of small average particle size, such as from about 0.01 micron to about 1 micron in average volume diameter as measured by the Brookhaven nanosize particle analyzer. Other effective amounts of resin can be selected.
  • a non-crosslinked resin is a resin that is substantially free of crosslinking, for example, a resin having substantially about zero percent cross linking to about 0.2 percent crosslinking, or a resin having less than about 0.1 percent crosslinking.
  • a crosslinked resin refers for example, to a crosslinked resin or gel comprising, for example, about 0.3 to about 20 percent crosslinking.
  • the resin selected can be a non-crosslinked resin such as, for example, a non-crosslinked resin comprising styrene:butylacrylate:beta-carboxyethyl acrylate, although not limited to these monomers, wherein, for example, the non-crosslinked resin monomers are present in an amount of from about 40 to about 95 percent styrene, from about 5 to about 60 percent butylacrylate, and about 0.05 parts per hundred to about 10 parts per hundred beta-carboxyethyl acrylate; or from about 60 to about 85 percent styrene, from about 15 to about 40 percent butylacrylate, and about 1 part per hundred to about 5 parts per hundred beta-carboxyethyl acrylate, by weight based upon the total weight of the monomers.
  • a non-crosslinked resin such as, for example, a non-crosslinked resin comprising styrene:butylacrylate:beta-carboxyethyl acrylate,
  • the resin may be selected to contain a carboxylic acid group selected, for example, from the group consisting of acrylic acid, methacrylic acid, itaconic acid, beta carboxy ethyl acrylate (beta CEA), fumaric acid, maleic acid, and cinnamic acid, and wherein, for example, a carboxylic acid is selected in an amount of from about 0.1 to about 10 weight percent of the total weight of the resin.
  • a carboxylic acid group selected, for example, from the group consisting of acrylic acid, methacrylic acid, itaconic acid, beta carboxy ethyl acrylate (beta CEA), fumaric acid, maleic acid, and cinnamic acid, and wherein, for example, a carboxylic acid is selected in an amount of from about 0.1 to about 10 weight percent of the total weight of the resin.
  • a second latex can be a high glass transition temperature (high Tg) resin comprising from about 40 to about 95 percent styrene, from about 5 to about 60 percent butylacrylate, and from about 0.05 parts per hundred to about 10 parts per hundred beta-carboxyethyl acrylate; or from about 65 to about 90 percent styrene, from about 10 to about 35 percent butyl acrylate, and from about 1 part per hundred to about 5 parts per hundred beta-carboxyethyl acrylate by weight based upon the total weight of the monomers.
  • high Tg high glass transition temperature
  • the process provides a first resin (resin A) comprising a non-crosslinked resin having a first Tg of about 46°C to about 56°C, about 48°C to about 54°C, or about 51°C, and a second non-crosslinked resin (resin B) having a high Tg (high Tg being for example a glass transition temperature that is from about 5°C to about 10°C higher than the Tg of the first resin) of for example, at Tg of about 54°C to about 65°C, about 56°C to about 64°C, or about 59°C.
  • first resin comprising a non-crosslinked resin having a first Tg of about 46°C to about 56°C, about 48°C to about 54°C, or about 51°C
  • a second non-crosslinked resin (resin B) having a high Tg high Tg being for example a glass transition temperature that is from about 5°C to about 10°C higher than the Tg of the first resin
  • latex polymer or resin particles include known polymers selected from the group consisting of styrene acrylates, styrene methacrylates, butadienes, isoprene, acrylonitrile, acrylic acid, methacrylic acid, beta-carboxy ethyl acrylate, polyesters, poly(styrene-butadiene), poly(methyl styrene-butadiene), poly(methyl methacrylate-butadiene), poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene), poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene), poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene), poly(butyl acrylate-butadiene), poly(styrene-isoprene), poly(methyl styrene-is
  • the resin particles selected can be prepared by, for example, emulsion polymerization techniques, including semicontinuous emulsion polymerization methods, and the monomers used in such processes can be selected from, for example, styrene, acrylates, methacrylates, butadiene, isoprene, and optionally acid or basic olefinic monomers, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, quaternary ammonium halide of dialkyl or trialkyl acrylamides or methacrylamide, vinylpyridine, vinylpyrrolidone, vinyl-N-methylpyridinium chloride, and the like.
  • emulsion polymerization techniques including semicontinuous emulsion polymerization methods
  • the monomers used in such processes can be selected from, for example, styrene, acrylates, methacrylates, butadiene, isoprene, and optionally acid or basic olefinic monomers, such as acrylic acid, methacryl
  • the presence of acid or basic groups in the monomer or polymer resin is optional, and such groups can be present in various amounts of from about 0.1 to about 10 percent by weight of the polymer resin.
  • Chain transfer agents such as dodecanethiol or carbon tetrabromide, can also be selected when preparing resin particles by emulsion polymerization.
  • Other processes of obtaining resin particles of from about 0.01 micron to about 1 micron can be selected from polymer microsuspension process, such as illustrated in U.S. Patent 3,674,736 , the disclosure of which is totally incorporated herein by reference, polymer solution microsuspension process, such as disclosed in U.S. Patent 5,290,654 , the disclosure of which is totally incorporated herein by reference, mechanical grinding process, or other known processes.
  • the toner processes disclosed herein comprise preparing a non-crosslinked latex resin (resin A) comprising, for example, styrene:butylacrylate:beta-carboxyethyl acrylate (monomers A, B, and C), by emulsion polymerization, in the presence of an initiator, a chain transfer agent, and surfactant.
  • resin A non-crosslinked latex resin
  • monomers A, B, and C styrene:butylacrylate:beta-carboxyethyl acrylate
  • the amount and composition of the resin monomers comprise, for example, from about 70 to about 90 percent styrene, from about 10 to about 30 percent butyl acrylate, and from about 0.5 to about 10 parts per hundred beta-carboxyethyl acrylate, or from about 76.5 percent styrene, 23.5 percent butyl acrylate, and 3 parts per hundred beta-carboxyethyl acrylate.
  • the amounts of initiator such as for example, sodium persulfate, potassium persulfate, or ammonium persulfate, can be selected in the range of from about 0.5 to about 5.0 percent by weight of the monomers.
  • the amount of chain transfer agent used can be selected in the range of from about 0.5 to about 5.0 percent by weight of the monomers A and B.
  • the surfactant can be an anionic surfactant, and can be selected in the range of from about 0.7 to about 5.0 percent by weight of the aqueous phase.
  • the monomers are polymerized under starve fed conditions as referred to in Xerox patents such as U.S. Patent 6,447,974 , U.S. Patent 6,576,389 , U.S. Patent 6,617,092 , and U.S. Patent 6,664,017 , which are hereby totally incorporated by reference herein, to provide latex resin particles having a diameter in the range of from about 100 to about 300 nanometers.
  • the molecular weight of the latex resin A can be, for example, about 30,000 to about 37,000, although not limited.
  • the onset glass transition temperature (Tg) of the resin A is from about 46°C to about 56°C, from about 48°C to about 54°C, or about 51 °C.
  • the amount of carboxylic acid groups can be selected at from about 0.05 to about 5.0 parts per hundred of the resin monomers A and B.
  • the molecular weight of the resin A obtained is about 34,000, and the molecular number is about 11,000, providing a non-crosslinked latex resin A having a pH of about 2.0.
  • a high Tg non-crosslinked latex resin (resin B) can be selected comprising styrene:butylacrylate:beta-carboxyethyl acrylate, again termed herein monomers A, B, and C, by an emulsion polymerization, in the presence of initiator, a chain transfer agent, and surfactant.
  • the composition of the monomers A:B:C can be selected as comprising from about 70 to about 90 percent styrene, from about 10 to about 30 percent butylacrylate, and from about 0.05 parts per hundred to about 10 parts per hundred beta-carboxyethyl acrylate, or about 81.7 % styrene, about 18.3% butyl acrylate, and about 3.0 parts per hundred beta-carboxyethyl acrylate.
  • the amounts of initiator such as sodium or ammonium persulfate, can be selected, for example, in the range of from about 0.5 to about 3.0 percent by weight of the monomers.
  • the amount of chain transfer agent used can be selected, for example, in the range of from about 0.5 to about 3.0 percent by weight based upon the weight of the monomers A and B.
  • the surfactant used can be an anionic surfactant, and can be selected in the range of from about 0.7 to about 5.0 percent by weight of the aqueous phase.
  • the emulsion polymerization is conducted under a starve fed polymerization as referenced, for example, in the Xerox patents referred to above, to provide latex resin particles which are selected in the size range of from about 100 nanometers to about 300 nanometers volume average particle diameter.
  • the molecular weight of the latex resin B is from about 30,000 to about 40,000, or from about 34,000, the molecular number is about 11,000, providing a non-crosslinked latex resin B having a pH of about 2.0.
  • the onset Tg of the high Tg resin B is from about 5°C to about 10°C higher than the Tg of resin A, or alternately, from about 54°C to about 65°C, from about 56°C to about 64°C, or about 59°C.
  • the amount of carboxylic acid groups can be selected at from about 0.05 to about 5.0 parts per hundred of the resin monomers A and B.
  • anionic surfactants suitable for use in the resin latex dispersion can include, for example, sodium dodecylsulfate (SDS), sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, dialkyl benzenealkyl, sulfates and sulfonates, adipic acid, available from Aldrich, NEOGEN RK TM , NEOGEN SC TM from Daiichi Kogyo Seiyaku or TAYCAPOWER BN2060 commercially available from Tayca Corporation or Dowfax available from DuPont and the like.
  • An effective concentration of the anionic surfactant generally employed can be, for example, from about 0.01 to about 10 percent by weight, and more specifically, from about 0.1 to about 5 percent by weight of monomers used to prepare the toner polymer resin.
  • nonionic surfactants that can be included in the resin latex dispersion include, for example, polyvinyl alcohol, polyacrylic acid, methalose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxypoly(ethyleneoxy) ethanol, available from Rhodia as IGEPAL CA-210 TM , IGEPAL CA-520 TM , IGEPAL CA-720 TM , IGEPAL CO-890 TM , IGEPAL CO-720 TM , IGEPAL CO-290 TM , IGEPAL CA-210 TM ,
  • a suitable concentration of the nonionic surfactant can be, for example, from about 0.01 to about 10 percent by weight, or from about 0.1 to about 5 percent by weight of monomers used to prepare the toner polymer resin.
  • the pigment dispersion can comprise pigment particles dispersed in an aqueous medium with a nonionic dispersant/surfactant.
  • a dispersant having the same polarity as that of the resin latex dispersion can also be used.
  • additional surfactants which may be added optionally to the aggregate suspension prior to or during the coalescence to, for example, prevent the aggregates from growing in size, or for stabilizing the aggregate size, with increasing temperature
  • anionic surfactants such as sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, dialkyl benzenealkyl, sulfates and sulfonates, adipic acid, available from Aldrich, NEOGEN R TM , NEOGEN SC TM available from Daiichi Kogyo Seiyaku, and the like, among others.
  • acids examples include, for example, nitric acid, sulfuric acid, hydrochloric acid, acetic acid, citric acid, trifluro acetic acid, succinic acid, salicylic acid and the like, and which acids are in embodiments utilized in a diluted form in the range of from about 0.5 to about 10 weight percent by weight of water, or in the range of from about 0.7 to about 5 weight percent by weight of water.
  • Introducing the sequestering or complexing component comprises in embodiments, introducing an organic complexing component selected from the group consisting of ethylenediaminetetraacetic acid, gluconal, sodium gluconate, potassium citrate, sodium citrate, nitrotriacetate salt, humic acid, and fulvic acid; salts of ethylenediaminetetraacetic acid, gluconal, sodium gluconate, potassium citrate, sodium citrate, nitrotriacetate salt, humic acid, and fulvic acid, alkali metal salts of ethylenediaminetetraacetic acid, gluconal, sodium gluconate, potassium citrate, sodium citrate, nitrotriacetate salt, humic acid, and fulvic acid; sodium salts of ethylenediaminetetraacetic acid, gluconal, sodium gluconate, tartaric acid, gluconic acid, oxalic acid, polyacrylates, sugar acrylates, citric acid, potassium citrate, sodium citrate,
  • Inorganic complexing components can be selected from the group consisting of sodium silicate, potassium silicate, magnesium sulfate silicate, sodium hexameta phosphate, sodium polyphosphate, sodium tripolyphosphate, sodium trimeta phosphate, sodium pyrophosphate, bentonite, and talc, and the like.
  • Organic and inorganic complexing components can be selected in an amount of about 0.01 weight percent to about 10.0 weight percent, or from about 0.4 weight percent to about 4.0 weight percent based upon the total weight of the toner.
  • coagulants include cationic surfactant, for example, dialkyl benzenealkyl ammonium chloride, lauryl trimethyl ammonium chloride, alkylbenzyl methyl ammonium chloride, alkyl benzyl dimethyl ammonium bromide, benzalkonium chloride, cetyl pyridinium bromide, C12, C15, C17 trimethyl ammonium bromides, halide salts of quaternized polyoxyethylalkylamines, dodecylbenzyl triethyl ammonium chloride, MIRAPOL and ALKAQUAT available from Alkaril Chemical Company, SANIZOL B (benzalkonium chloride), available from Kao Chemicals, and the like, and mixtures thereof.
  • cationic surfactant for example, dialkyl benzenealkyl ammonium chloride, lauryl trimethyl ammonium chloride, alkylbenzyl methyl ammonium chloride, alkyl benzyl
  • Inorganic cationic coagulants include, for example, poly-aluminum chloride (PAC), poly-aluminum sufosilicate, aluminum sulfate, zinc sulfate, magnesium sulfate, chlorides of magnesium, calcium, zinc, beryllium, aluminum, sodium, other metal halides including monovalant and divalent halides.
  • the coagulant can be present in an aqueous medium in an amount of from, for example, from about 0.05 to about 10 percent by weight, or from about 0.075 to about 5.0 percent by weight of total solids in the toner.
  • the coagulant may also contain minor amounts of other components, for example nitric acid.
  • the coagulant may comprise a mixture of both an inorganic and an organic coagulant including, for example, PAC and SANIZOL B, aluminum sulfate and SANIZOL B, etc.
  • Such mixtures of coagulants are also preferably used in an aqueous medium, each present in an amount of from, for example, from about 0.05 to about 5.0 percent by weight of total solids in the toner.
  • a colorant dispersion is selected, for example, comprising a cyan, magenta, yellow, or black pigment dispersion of each color in an anionic surfactant or optionally a non-ionic dispersion to provide, for example, pigment particles having a volume average particle diameter size selected of from about 50 nanometers to about 500 nanometers.
  • the surfactant used to disperse each colorant can be, for example, an anionic surfactant such as Neogen RK TM .
  • An Ultimaizer equipment can be used to provide the pigment dispersion, although media mill or other means can be utilized.
  • the toner can also comprise a colorant.
  • Suitable colorants include pigments, dyes, mixtures of pigments and dyes, mixtures of pigments, mixtures of dyes, and the like.
  • the colorant comprises carbon black, magnetite, black, cyan, magenta, yellow, red, green, blue, brown, mixtures thereof, selected for example, in an amount of from about 1 to about 25 percent by weight based upon the total weight of the composition.
  • Colorants can be selected in the form of a pigment dispersion comprising pigments particles having a size in the range of from about 50 to about 500 nanometers, water, and an anionic surfactant or polymeric stabilizer.
  • pigments are available in the wet cake or concentrated form containing water, and can be easily dispersed utilizing a homogenizer, or simply by stirring, ball milling, attrition, or media milling.
  • pigments are available only in a dry form, whereby dispersion in water is effected by microfluidizing using, for example, a M-110 microfluidizer or an Ultimaizer and passing the pigment dispersion from about 1 to about 10 times through the chamber, or by sonication, such as using a Branson 700 sonicator, or a homogenizer, ball milling, attrition, or media milling with the optional addition of dispersing agents such as the aforementioned ionic or nonionic surfactants.
  • the above techniques can also be applied in the presence of a surfactant.
  • Specific colorants that may be used include, Paliogen Violet 5100 and 5890 (BASF), Normandy Magenta RD-2400 (Paul Ulrich), Permanent Violet VT2645 (Paul Ulrich), Heliogen Green L8730 (BASF), Argyle Green XP-111-S (Paul Ulrich), Brilliant Green Toner GR 0991 (Paul Ulrich), Lithol Scarlet D3700 (BASF), Toluidine Red (Aldrich), Scarlet for Thermoplast NSD Red (Aldrich), Lithol Rubine Toner (Paul Ulrich), Lithol Scarlet 4440, NBD 3700 (BASF), Bon Red C (Dominion Color), Royal Brilliant Red RD-8192 (Paul Ulrich), Oracet Pink RF (Ciba Geigy), Paliogen Red 3340 and 3871 K (BASF), Lithol Fast Scarlet L4300 (BASF), Heliogen Blue D6840, D7080, K7090, K6910 and L7020 (BASF), Sudan Blue OS (BASF), Neopen Blue
  • Additional useful colorants include pigments in water-based dispersions such as those commercially available from Sun Chemical, for example SUNSPERSE BHD 6011 (Blue 15 Type), SUNSPERSE BHD 9312 (Pigment Blue 15), SUNSPERSE BHD 6000 (Pigment Blue 15:3 74160), SUNSPERSE GHD 9600 and GHD 6004 (Pigment Green 7 74260), SUNSPERSE QHD 6040 (Pigment Red 122), SUNSPERSE RHD 9668 (Pigment Red 185), SUNSPERSE RHD 9365 and 9504 (Pigment Red 57, SUNSPERSE YHD 6005 (Pigment Yellow 83), FLEXIVERSE YFD 4249 (Pigment Yellow 17), SUNSPERSE YHD 6020 and 6045 (Pigment Yellow 74), SUNSPERSE YHD 600 and 9604 (Pigment Yellow 14), FLEXIVERSE LFD 4343
  • HOSTAFINE Yellow GR HOSTAFINE Black T and Black TS
  • HOSTAFINE Blue B2G HOSTAFINE Rubine F6B
  • magenta dry pigment such as Toner Magenta 6BVP2213 and Toner Magenta E02 which can be dispersed in water and/or surfactant prior to use.
  • magnetites such as Mobay magnetites MO8029, M08960; Columbian magnetites, MAPICO BLACKS and surface treated magnetites; Pfizer magnetites CB4799, CB5300, CB5600, MCX6369; Bayer magnetites, BAYFERROX 8600, 8610; Northern Pigments magnetites, NP-604, NP-608; Magnox magnetites TMB-100 or TMB-104; and the like or mixtures thereof.
  • pigments include phthalocyanine HELIOGEN BLUE L6900, D6840, D7080, D7020, PYLAM OIL BLUE, PYLAM OIL YELLOW, PIGMENT BLUE 1 available from Paul Ulrich & Company, Inc., PIGMENT VIOLET 1, PIGMENT RED 48, LEMON CHROME YELLOW DCC 1026, E.D. TOLUIDINE RED and BON RED C available from Dominion Color Corporation, Ltd., Toronto, Ontario, NOVAPERM YELLOW FGL, HOSTAPERM PINK E from Hoechst, and CINQUASIA MAGENTA available from E.I. DuPont de Nemours & Company, and the like.
  • magentas examples include, for example, 2,9-dimethyl substituted quinacridone and anthraquinone dye identified in the Color Index as CI 60710, CI Dispersed Red 15, diazo dye identified in the Color Index as CI 26050, CI Solvent Red 19, and the like or mixtures thereof.
  • cyans include copper tetra(octadecyl sulfonamide) phthalocyanine, x-copper phthalocyanine pigment listed in the Color Index as CI74160, CI Pigment Blue, and Anthrathrene Blue identified in the Color Index as DI 69810, Special Blue X-2137, and the like or mixtures thereof.
  • yellows that may be selected include diarylide yellow 3,3-dichlorobenzidene acetoacetanilides, a monoazo pigment identified in the Color Index as Cl 12700, Cl Solvent Yellow 16, a nitrophenyl amine sulfonamide identified in the Color Index as Foron Yellow SE/GLN, CI Dispersed Yellow 33 2,5-dimethoxy-4-sulfonanilide phenylazo-4'-chloro-2,4-dimethoxy acetoacetanilide, and Permanent Yellow FGL.
  • Colored magnetites such as mixtures of MAPICO BLACK and cyan components may also be selected as pigments.
  • the toner may also include known charge additives in effective amounts such as, from about 0.1 to about 5 weight percent, such as alkyl pyridinium halides, bisulfates, the charge control additives of U.S. Patents 3,944,493 ; 4,007,293 ; 4,079,014 ; 4,394,430 and 4,560,635 , the disclosures of which are totally incorporated herein by reference, and the like.
  • charge additives in effective amounts such as, from about 0.1 to about 5 weight percent, such as alkyl pyridinium halides, bisulfates, the charge control additives of U.S. Patents 3,944,493 ; 4,007,293 ; 4,079,014 ; 4,394,430 and 4,560,635 , the disclosures of which are totally incorporated herein by reference, and the like.
  • suitable additives include zinc stearate and AEROSIL R972 ® available from Degussa in amounts of from about 0.1 to about 2 percent which can be added during the aggregation process or blended into the formed toner product.
  • developer and imaging processes including a process for preparing a developer comprising preparing a toner composition with the toner processes illustrated herein and mixing the resulting toner composition with a carrier.
  • Developer compositions can be prepared by mixing the toners obtained with the processes of the present disclosure with known carrier particles, including coated carriers, such as steel, ferrites, and the like, reference U.S. Pat. Nos. 4,937,166 and 4,935,326 , the disclosures of which are totally incorporated herein by reference, using, for example from about 2 to about 8 percent toner concentration.
  • the carriers selected may also contain dispersed in the polymer coating a conductive compound, such as a conductive carbon black and which conductive compound is present in various suitable amounts, such as from about 15 to about 65, or from about 20 to about 45 weight percent by weight of total solids.
  • a conductive compound such as a conductive carbon black and which conductive compound is present in various suitable amounts, such as from about 15 to about 65, or from about 20 to about 45 weight percent by weight of total solids.
  • Imaging processes comprise, for example, preparing an image with an electrophotographic or xerographic device comprising a charging component, an imaging component, a photoconductive component, a developing component, a transfer component, and a fusing component; and wherein the development component comprises a developer prepared by mixing a carrier with a toner composition prepared with the toner processes illustrated herein; an imaging process comprising preparing an image with an electrophotographic or xerographic device comprising a charging component, an imaging component, a photoconductive component, a developing component, a transfer component, and a fusing component; wherein the development component comprises a developer prepared by mixing a carrier with a toner composition prepared with the toner processes illustrated herein; and wherein the electrophotographic or xerographic device comprises a high speed printer, a black and white high speed printer
  • the size of the toner particles can be, for example, from about 1 to about 25 microns, from about 3 microns to about 9 microns, more specifically, from about 4 microns to about 6 microns or about 5 microns.
  • the fractionated and/or distilled wax also was determined to have a degree of crystallinity as measured on the cooling cycle of from about 100 to about 55°C. These measurements were under the conditions wherein the cooling rate was 2°C/min (first scan).
  • the heat of recrystallization (Hrc) in J/g during cooling was equal to or greater than 150 J/g (see Figure 1).
  • the wax also was determined to have a degree of crystallinity as measured on the cooling cycle of from about 60 to about 100°C. These measurements were under the conditions wherein the heating rate was 10°C/min (second scan). The heat of enthalpy (Hm) in J/g during heating was equal to or greater than 150 J/g (see Figure 1). The percent crystallinity was then calculated from the following expression:
  • Figure 1 demonstrates the results of testing of BP X1214 from Baker Petrolite.
  • the waxes were tested for degree of crystallinity using X-ray diffraction.
  • the samples were Polywax 655, X1214 and X1242 (all three are crystalline polyethylene waxes from Baker Petrolite).
  • the waxes had a degree of crystallinity as measured by X-ray diffraction (Xc) of from about 55 to about 100 percent crystallinity using a Rigaku Miniflex instrument, manufactured by Rigaku Corporation.
  • the instrument was fitted with a Cu-target and operated at a tube voltage of 3KV with a tube current output of 30 mA. The measurement range was between 5 ° 2-theta to about 35 ° 2-theta.
  • the viscosity of the wax was measured using a temperature sweep conducted at 2°C/min, as measured on a Rheometric Scientific RFS 3 fluids spectrometer equipped with a Peltier cell and using the cone and plate geometry at a nominal gap of 53 microns and a 0.04 radians, 50 mm cone.
  • the viscosity - temperature relationship can be represented by: ⁇ cp ⁇ 10 27 - 0.25 ⁇ T ⁇ where ⁇ 92 ⁇ °C T ⁇ 100 ⁇ °C
  • Figure 3 represents the useful coalescence temperature ranges as well as the viscosity ranges.
  • the experimental procedure was a Dynamic Temperature Steps test. The test was started at an initial temperature of 100°C followed by a decrease in temperature to 84°C and back to 100°C in 2°C steps. The soak time between each temperature step was 150 seconds to allow for temperature equilibration. The strain amplitude was varied to maintain the data within the operating limits of the transducer.
  • the equation defines the slope and what the viscosity of the wax for a given coalescence temperature should be. For example, if the coalescence temperature was 94°C, then using the above equation, viscosity (cp) of the wax is calculated to be ⁇ 103.5. And hence the fit of the slope.
  • Solutions of wax were prepared by dissolving from about 40 to about 60 mG of wax into 15 mL of warm (80°C) toluene. This solution was injected warm (80°C) using a hot syringe. Alkane distribution identification was obtained by injecting alkane mixes of C13, 15, 20, and 36.

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2015142A3 (de) * 2007-07-12 2010-08-25 Xerox Corporation Tonerzusammensetzungen
US7910276B2 (en) 2007-07-12 2011-03-22 Xerox Corporation Toner compositions
EP2306968B1 (de) * 2008-06-25 2016-12-07 Chanel Parfums Beauté Ein silikonacrylat und ein polyesterwachs enthaltende kosmetische zusammensetzung

Also Published As

Publication number Publication date
CA2567262C (en) 2010-08-31
US7686939B2 (en) 2010-03-30
CA2567262A1 (en) 2007-05-14
KR101320906B1 (ko) 2013-10-21
BRPI0604756B1 (pt) 2020-12-22
BRPI0604756A (pt) 2007-08-28
CN1966622A (zh) 2007-05-23
CN1966622B (zh) 2012-09-19
KR20070051727A (ko) 2007-05-18
DE602006012150D1 (de) 2010-03-25
EP1785773B1 (de) 2010-02-10
JP2007138167A (ja) 2007-06-07
US20070131580A1 (en) 2007-06-14

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